JPS60202811A - Perfume composition containing dihydro-and/or tetrahydro-naphthols and perfumed products - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides fragrance materia
Perfumes containing dihydronaphthol derivatives and/or tetrahydronaphthol derivatives as l)
e) compositions and perfumed with these compounds or perfume compositions containing these compounds;
) relating to goods.

There is increasing interest in the production and use of synthetic fragrance materials because, unlike substances of natural origin, synthetic products can always be produced in desired quantities and of uniform quality.

In particular, there is a need for synthetic fragrances with natural odor characteristics.

Leather has a characteristic, highly complex but highly respected odor.
Medodour). Previously, the smell of leather (1
gαtherodour) could only be attempted by combining a number of raw materials known per se in the perfumery industry. Traditionally important ingredients of leather odor compositions are birchthal oil and substituted phenols and phenol ethers such as p-tert, butyl-phenol, tert.

Butyl-metacresol and its methyl ether (S, Arctandttr, perfum
e and Flavor Chttmicals, M
onograph number 504 s 42
9 αnd 430). However, a truly satisfying leather odor could not be obtained with hitherto known ingredients.

(wherein the dotted line represents a carbon-carbon single bond or double bond, provided that not more than one of them is a double bond, and R, R, and R3 independently represent a methyl group. The dihydro- and tetrahydro-1-naphthol derivatives of
oty) was found to be a strong and stable aromatic substance. Particularly preferred are the above compounds in which both R1 and R1 are methyl groups, or only R1 is a methyl group, or all are hydrogen atoms.

The compounds of the invention can be used on their own or in combination with ingredients useful for that purpose to impart a delicate and very natural leathery odor to all kinds of articles and materials. Very suitable. The compound imparts a leather-like feel to the fragrance composition.
It can also be advantageously used to provide an ethery aspect).

Although most of the compounds of the invention are known per se in the chemical literature, they are still unknown to the perfume industry. Tetrahydro-1-naphthyl ethyl ether has a sweet (gwggt), warm floral (Fαr) odor that is in no way similar to the odor of the compounds of this invention.
mfloταl) and a weak woody odor (wood
Arctander (
A 2921 ). Sara K, Ar6tα
ndttr reports that this ether is of little interest in the perfume industry.

West German Patent Application Publication no.
It has been reported that it is effective in preventing The compound is described as having a pleasant medicinal odor which is said to make additional labeling of shampoos and hair lotions containing this compound unnecessary. However, although medicinal odor is appropriate for certain types of medicinal products such as anti-dandruff shampoos, it is not actually recognized by many people, and therefore this description does not imply that this compound is used in perfumery production. There is no suggestion that it is of general utility. More specifically, it is not suggested to be useful in imparting a subtle leathery odor.

Compounds of the invention can be made according to methods generally known in the art. Such a method is, for example, O
rganic 5yntlytsis, Co11.
Voltt, meRl, pages 887-9+
J, Org, Ch, em, Vol, 36 (197
1) pages 3345-3349+ J, Am
, Chetn, Soa, .

VOl, 61 (1939) pdgg8765-767
+Described in West German Official Gazette No. 2333847 and the references cited therein.

The term "fragrance composition" refers to a composition that can be dissolved in a suitable solvent or mixed with a powdered matrix and used to impart a desired odor to the skin and/or to various products. Used to mean a mixture of fragrances and optionally auxiliary substances that can be used. Examples of such products are soaps, detergents, air fresheners, room sprays, bombers. , candle,
Cosmetics, such as creams, ointments, colognes
ognes), pre-and a#r 5have 1ot
ions), talcum powder, body odor remover (body
deodorants) and antiperspirants. The compounds according to the invention are also particularly suitable for imparting a leather odor to products of all kinds, especially leather substitutes.

Fragrance substances and mixtures thereof which can be used in combination with the compounds of the invention for the preparation of perfume compositions include natural products such as essential oils, absolutes, etc.
), resinoids), resins, aromatic wax components extracted from flowers (concretts)
synthetic aromatic substances such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, saturated or unsaturated and aliphatic, carbocyclic or heterocyclic. , ketals, nitriles, and the like.

Fragrances to be used in combination with the compounds according to the invention include geraniol, geranyl acetate, -1h+1++
1-2-t;;+ノ【War-啼-11-μRol, citronellol, citronellyl acetate, dihydromircenol,
Dihydro-myrcenyl acetate, tetrahydromyrcenol, terpineol, tilvinyl acetate, nopol, nobil acetate, β-7yenyl-ethanol, β-phenyl acetate
Ethyl, benzyl alcohol, benzyl acetate, benzyl salicylate, benzyl benzoate, amyl salicylate, styralyl acetate,
Dimethyl-benzyl carbinol, trichloromethyl-phenyl-carbinyl acetate (triOhl orome
thyl-phenyl-carbinyl ace
tate), acetic acid p-tgtrt.

Butyl-cyclohexyl, isononyl acetate, petiveryl acetate, petiverol, α-hexyl-cinnamaldehyde, 2-methyl-3(p-tgrt, butylphenyl)-furopanal, 2-methyl-3-(pi misopropylphenyl-prono (Naar, 3- (p-tert
, butylphenyl)-pronoxol, tricyclodecenyl acetate, tricyclodecenyl propionate, 4-(4
-Hydroxy-4-methylpentyl)-cyclohex-3-enecarb 7/l/dehyde (4-(4-hydro
yay-4-mttthyl-pentyl)-cyt
ylohtt:t-3-gna:l,4-acetoxy-
3-pentyl-tetrahydrobyran, 3-carboxymethyl-2-pentyl-cyclopentane, 2-n-heptyl-cyclopentanone, 3-methyl-2-pentylcyclopentan-2-one, n-decanal, n-dodecanal , dec-9-eno/l/ (dec-9-eno
l), 7! / -? Sea: x f, TI/
Isobutyrate, phenyl-acetaldehyde dimethyl acetal, phenyl-acetaldehyde phodiethyl acetal, geranyl nitrile, citronellyl nitrile,
cadryl acetattr
, 3-iso-camphyyl-cyclohexanol, cedryl methyl ether, isolon
gifolinontt), opavinitrile, aubevin, heliothrobin, coumarin, eugenol, vanillin, diphenyl oxide, hydroxy-citronellal, ionones, methylionones, in-methyl-ionones, irones, cis-hex-3-ethyl/ −
/l/(cis-hex-3-enol) and its esters, indan musks, tetralin musks, inchroman musks, macrocyclic ketones, macrolactone musks (
macrolactontttmasks), ethylene brasilate (eth, yl enebrα8ri1at
tt), aromatic nitro musks.

Auxiliaries and solvents that can be added to perfume compositions containing the compounds according to the invention are, for example, ethanol, isoglopanol, diethylene glycol monoethyl ether, diethyl phthalate and the like.

The amount of a compound of the invention that can be used in a perfume composition or product to be perfumed can vary within a wide range and depends, for example, on the type of product for which the compound is used, on other products in the composition. depending on the nature and amount of the ingredients and the desired odor effect. Thus, only arbitrary limits can be given, but this gives the person skilled in the art sufficient information to be able to use the compound for his own purposes. In most cases, only 0.1 weight in the fragrance composition! This will produce a clearly perceptible odor effect. On the other hand, amounts up to 90 inches or more can be used in compositions for specific leather odors.

In products scented with the fragrance composition according to the invention,
The concentration depends on the amount of composition used in the product and is therefore proportionally lower.

The following examples illustrate the preparation and use of compounds according to the invention, but are not intended to limit the invention thereto.

Example I 5.8-dihydro-1-naphthol was added to OrganicS
synthesis, Ca1l, Vol, W, pa (H
s 8 8 7-9.

The above compound has a soft animalic (α
It has a pleasant leather-like odor.

5.8-dihydro-1-naphthol in DMSO
rt, B% OK 7,8-dihydro-1- by heating at 95°C for 10 hours with a 1.1 molar equivalent solution.
1 part naphthol and 5.6-sihydro! - isomerized to a mixture of 2 parts of naphthol.

The mixture has a pleasant odor very similar to that of 5,8-dihydro-1-naphthol.

5.8-dihydro-1-naphthol with Organic5
synthesis, Co11. Vol, W, pag
e, 8 B? Hydrogenation was performed as described in 1-9 to obtain tetrahydro-1-naphthol. This compound has a very strong and very distinct leather odor.

5.8-dimethyl-tetrahydro-1-naphthol to J
, Org, Chgtn,, Vol, 36 (197
1) Produced as described on pages 3345-3349.

This compound has a slight camphor nuance (sli
ght camphoraceous nuance)
It has a distinct leathery odor.

EXAMPLE 2-Methyl-tetrahydro-1-naphthol was prepared as follows: Tetrahydro-1-naphthol 1301I (0.88 mol) was dissolved in 100 m/ml of ethanol. Diethylamine 70.51! (0.96 mol) at 10-15℃
It was added as an aqueous solution.

Thereafter, 4.59 (0.95 mol) of 35 thiol was slowly added while maintaining the temperature of the mixture at 10-15°C. Stirring was continued for 4 hours, during which time the temperature was 65°C.
rose to

After cooling to room temperature, the layers were separated and the aqueous layer was extracted twice with toluene. -The combined organic layers were washed with water and dried over M (1504).

The residue obtained after evaporation of the solvent was distilled to yield 89 2-diethylamino-tetrahydro-1-naphthol.

The product 4&59 was dissolved in 100+aJ of ethanol LA:I, and 4.89g of 5'4Pd/C catalyst and 2.4g of p-toluenesulfonic acid were added to tJ.

The mixture was hydrogenated at 45° C. for 4 hours under a hydrogen pressure of 300 kPa. The catalyst was then removed by filtration and the solvent was removed. The residue was dissolved in 100 ml of water and extracted with ether. The aqueous layer was acidified with hydrochloric acid and extracted once more with ether. - The combined organic layers were washed with dilute hydrochloric acid, dried over MgSO4 and evaporated. The residue was distilled to give the desired 2-methyl-tetrahydro-1-naphthol in 69% yield.

This compound has a strong leathery odor with animalic and slightly camphor nuances.

Example ■6 A fragrance composition for Men's cologne was prepared according to the following procedure.

Acetyl cedrene 200 parts by weight Bergamot oil 190 z (Bergamot oil) Lemon oil 90 l (Lemon oil) α-Hexylucinnamaldehyde'90 I Lavandin oil 60 N (Lavandin oil) Patchouli oil 5 0 overlapping section (Patchouli oil) Methyl dihydrojasmonate 50 N (Mttth
yl dhydrojustonate) 5-acetyl-3-inpropyl 30 1-1,1,2.6-
Chitra methyl-indane synthetic mugette 30 1 (Mrbgwet 5yntettC) Isolongiphoranone 30 l Subicara bender oil 30 1 (Aapic oil) Musk ketone 20 1 Labdanum rasinoid 20 1 (Ylang) oil) Mentovllz 10# Mustoucien Absolute 101 (Jfousse do cheng abttolu
te) Isobutylquinoline *10 1 Galbanum oil 10 parts by weight Styraryl acetate 51 Clove oil 51 Undecylenaldehyde 51 * Methyl-nonyl-acetaldehyde 51 Tetrahydro-1-naphthol 30 z 1000 Parts by weight*10% by weight dissolved in diethylene glycol monoethyl ether 5°8-dihydro-1-naphthol or 7,8% by weight of 30 parts of tetrahydro-1-naphthol prepared according to Example 2 in the above process A comparable composition was prepared by substituting 60 parts by weight of a mixture of - and 5,6-dihydro-1-naphthol.

Example ■ A fragrance composition for an aftershave lotion was prepared according to the following recipe: Cedryl acetate 230 parts by weight Benzyl salicylate 90 l Musk ketone 53 z Cutulin 30 z Methyl dihydrojasmonate 30 z Synthetic amber
25 1 (J4rnber 5ynthetic) (Bαsil
oil) Origanum oil 21 (Origanum oil) 1000 parts by weight In the above formulation, tetrahydro-1-naphthol 50
Comparable compositions were prepared by substituting 80 parts by weight of 2-methyl-nato-2hydro-1-naphthol or 5,8-dimethyl-tetrahydro-1-naphthol, respectively, prepared according to Examples Plate and I. .

Example V An aftershave lotion numbered with a composition according to Example W was prepared according to the following recipe: A. 0.3 parts by weight of 1-menthol 30.0 parts by weight of propylene glycol 535, 0 parts by weight. of ethanol 2.0 parts by weight lactic acid 400, 0 parts by weight water (desalted) 0, 20 parts by weight perfume (Example ■) The compositions described in A, B and C were mixed separately. Mixture A, B, C
I got it.

Mixture B was added to mixture A with thorough stirring. Mixture C was then added and the whole was stirred to obtain a homogeneous mixture. Thus, a pleasant leather notebook (leat
A somewhat astringent aftershave lotion was obtained, with an odor characterized by the following.

1) BASF's trademark for 2.2',4,4'-tetrahydroxy-benzophenone; 2) BASF's trademark for the reaction product of hydrogenated castor oil and ethylene oxide.

SψAlbertus Van Fist der Weert @ Inventor Jokuhum Hofma Oler [273 GNEhuizenφHinde 11 Nanda Country 3817
PEX Amersford Jant□Bstraat 9

Claims (1)

[Claims] 1. Formula (wherein the dotted line represents a carbon-carbon single bond or double bond, provided that at most one of them is a double bond, R, , R, and R is independently a methyl group or a hydrogen atom).
Perfume compositions and perfumed products containing at least one s7tol derivative as a perfume component, characterized in that they contain seeds. Claims characterized in that they contain at least one dihydro- or tetrahydro-1-naphthol derivative bundle of formula I, in which Z R and R2 are methyl groups and Rs is a methyl group or a hydrogen atom Fragrance compositions/things and scented products as described in Scope 1. & R1 and R1 are hydrogen and R8 is a methyl group, at least one dihydro- or tetrahuman 4-1-naphthol derivative of formula I. Perfume compositions and perfumed products. 4. The fragrance composition and fragrance composition according to claim 1, characterized in that it contains a dihydro- or tetrahydro-1-naphthol derivative of formula (1), in which R1, R, and R8 are hydrogen atoms. products. & Formula described in any one of claims 1-4! dihydro- or tetrahydro-! 5. The fragrance composition according to any one of claims 1 to 4, characterized in that it contains at least 0.1% by weight of a 7-tall derivative. 6. The fragrance composition according to any one of claims 1-5 or claim 1-5 for scenting a product.
The formula described in any of Section 5! Use of dihydro- and nato-2hydro-1-naphthol derivatives.